Nitrogen doped a2nb4o11, process for preparation thereof, and method for degradation of organic pollutants

ABSTRACT

The present invention relates to nitrogen doped A 2 Nb 4 O 11 , which is represented by A 2 Nb 4 O 11-x N x , to a process for the preparation thereof, and to a method for degradation of organic pollutants. The nitrogen doped A 2 Nb 4 O 11  is a new photocatalyst for the photocatalytic degradation of organic pollutants in the waste water. The A 2 Nb 4 O 11-x N x  catalyst may be prepared by substituting some of the O elements of pure A 2 Nb 4 O 11  with N elements, and a process for the preparation thereof comprises a step of doping of nitrogen with a nitrogen source through a solid state reaction. The new nitrogen doped A 2 Nb 4 O 11  catalyst having a general formula A 2 Nb 4 O 11-x N x  has a narrower optical bandgap compared to pure A 2 Nb 4 O 11 , and therefore can be activated under the visible light range and it shows high efficiency in the degradation of organic pollutants.

TECHNICAL FIELD

The present invention relates to the field of photo-catalyst, particularly to nitrogen doped A₂Nb₄O₁₁, process for preparation thereof, and method for degradation of organic pollutants.

STATE OF THE ART

Organic pollutants in water have been causing serious environmental problems. Photocatalytic degradation of these pollutants using sunlight is an attractive solution to this global problem. At present, the most commonly used photocatalysts are semiconductors, such as ZnO,¹⁻⁶ TiO₂,⁷⁻⁹ BiWO₆,¹⁰ CdS,¹¹ Fe₂O₃,¹² and HNbO₃.¹³ These semiconductors, however, can only absorb UV light due to their large band gaps. For better utilization of sunlight and indoor illumination, Nb-based photocatalysts have recently been extensively studied because the layered perovskite type niobates can be excited by visible light.¹³⁻¹⁶

In 1981, Dion reported a family of layered perovskite type niobates, generally formulated as AM₂Nb₃O₁₀ (A=K, Rb, Cs; M=La, Ca, etc.), which show noticeable photocatalytic activity.¹⁴ Soon after that Yoshimura reported a layered perovskite type niobate, RbPb₂Nb₃O₁₀, that could photocatalytically generate H₂ from water by visible light.¹⁵ Recently, Wu reported K_(2-x)La₂Ti_(3-x)Nb_(x)O₁₀ and their protonated derivatives for water splitting under visible light.¹⁶ However, the use of layered perovskite type niobates as photocatalysts for the degradation of organic pollutant has received little attention until very recently, when Ye reported efficient photodegradation of Rhodamine B in water using nitrogen-doped lamellar niobic acid.¹³ Although these layered perovskite type niobates and their protonated derivatives show high photoactivity under visible light irradiation, the structures of these photocatalysts are generally not very stable and are susceptible to collapse even under atmospheric conditions.¹³⁻¹⁶

We are interested in the use of non-layered niobate salts as photocatalysts as we anticipate that they would be more robust than the layered niobates and their protonated derivatives. K₂Nb₄O₁₁ is constructed from NbO₆ octahedra and has a tetragonal tungsten bronze (TB) crystal structure with triangle, quadrilateral and pentagonal tunnels. The pentagonal and quadrilateral tunnels are occupied by cations and the triangle tunnels by Nb cations.¹⁷ It has been reported that Cu-doping of K₂Nb₄O₁₁ results in increased photocatalytic activity thr the degradation of acid red. G under UV irradiation.¹⁸

SUMMARY OF THE INVENTION

The present invention provides a nitrogen doped photocatalyst which is denoted as A₂Nb₄O₁₁—N, or represented by the following general formula (I)

A₂Nb₄O_(11-x)N_(x)  (I)

wherein

A is selected from the elements of IA group of the periodic table; and 0<x<1.

According to one aspect of the present invention, A in the general formula (I) is Li, Na, K, Rb or Cs. Most preferably, A is K.

According to one aspect of the present invention, the compound of the general formula (I) of the present invention has a tetragonal tungsten bronze crystal structure.

According to one aspect of the present invention, the compound of the general formula (I) of the present invention may be used as a photocatalyst. Preferably, said photocatalyst can be activated under visible lights.

The present invention further provides a process for the preparation of the compound of the general formula (I) of the present invention, comprising the steps of:

1) surface acidification of A₂Nb₄O₁₁, wherein A₂Nb₄O₁₁ is immerged in an acidic solution, filtered, washed and dried; and

2) nitrogen doping of A₂Nb₄O₁₁ to obtain A₂Nb₄O_(11-x)N_(x), wherein A₂Nb₄O₁₁ obtained in step 1) is mixed with a nitrogen source and heated, the product is washed to remove residue nitrogen source adsorbed on the surface of the product and dried.

The A₂Nb₄O_(11-x)N_(x) catalyst of the present invention is prepared by replacing some of the O elements in pure A₂Nb₄O₁₁ with N elements, and a process for the preparation thereof comprises a step of doping of nitrogen with a nitrogen source through a solid state reaction.

According to one aspect of the present invention, the nitrogen source in the above process may be an ammonium salt or a nitrogen-containing organic compound, such as ammonium carbonate or urea.

According to one aspect of the present invention, the acidic solution used in step 1) of the above process may be selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, or phosphoric acid. Preferably, the acidic solution has a concentration of 1-10 mol/L.

According to one aspect of the present invention, in step 1), the ratio of the weight of A₂Nb₄O₁₁ to the volume of the acidic solution may be from 1 g:10 ml to 1 g:600 ml.

According to one aspect of the present invention, in step 1), the duration of the immerging may be 10-96 h.

According to one aspect of the present invention, in step 1), the washing may be performed with distilled water; the drying may be performed under a temperature of 20-300° C., and the duration of the drying may be above 10 h.

According to one aspect of the present invention, in step 2), the weight ratio of A₂Nb₄O₁₁ and the nitrogen source may be from 1:0.5 to 1:1.0.

According to one aspect of the present invention, in step 2), the heating may be performed under a temperature of 300-600° C.

According to one aspect of the present invention, in step 2), the duration of the heating may be 1-10 h.

According to one aspect of the present invention, in step 2), the product may be washed with acetone and/or distilled water to remove residue nitrogen source, such as alkaline species, adsorbed on the surface of the product.

According to one aspect of the present invention, in step 2), the drying may be performed under a temperature of 20-300° C., and the duration of the drying may be 10-96 h.

A₂Nb₄O₁₁ used in step 1) of the present invention has a tetragonal tungsten bronze crystal structure. It may be obtained commercially, or may be prepared according to a process know in the art, or may be prepared according a process wherein A₂Nb₄O₁₁ is prepared by heating a mixture of Nb₂O₅ and A₂CO₃ for several hours. In said process, the heating may be performed under a temperature of 800-1200° C.; the duration of the hearing may be 8-50 h; and the ratio of Nb₂O₅ and A₂CO₃ may be from 3:1 to 1:10.

The present invention further provides a method for degradation of organic pollutants, comprising contacting the organic pollutants with the compound of the general formula (I) of the present invention. As used herein, the term “organic pollutants” generally refers to organic substances which may cause adverse effects to human health and the environment. Preferably, the organic pollutants are those difficult to decompose in waste water. As used herein, the organic pollutants difficult to decompose are organic compounds which may be present in waste water for a long time without decomposition under ambient conditions, such as Orange G (OG) and bisphenol A (BPA).

It has been proven that the new catalyst having a general formula A₂Nb₄O_(11-x)N_(x) has a narrower optical bandgap compared to pure A₂Nb₄O₁₁, and therefore can be activated under the visible light range and it shows high efficiency in the degradation of organic pollutants, especially organic pollutants difficult to decompose. In addition, the process for the synthesis of the nitrogen doped A₂Nb₄O₁₁ is simply and can be performed on a large scale, and the process for nitrogen doping is less expensive than conventional sputtering ones.

The present photocatalyst has the advantages of non-toxicity, chemical inertness, high stability under light irradiation, and high photo efficiency under visible light, and is therefore a superior photocatalyst.

BRIEF DESCRIPTION OF THE DRAWINGS

The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee. The present disclosure will become more fully understood from the detailed description given herein below for illustration only, and thus are not limitative of the present disclosure, and wherein:

FIG. 1. Molecular structures of OG and BPA and their UV-Vis absorption spectrum.

FIG. 2. XRD patterns of: A) K₂Nb₄O₁₁ B) K₂Nb₄O₁₁—N and C) standard K₂Nb₄O₁₁ (JCPDS 31-1059).

FIG. 3. SEM images of: A) K₂Nb₄O₁₁ and B) K₂Nb₄O₁₁—N.

FIG. 4. XPS spectra in the whole energy range. A) K₂Nb₄O₁₁ and B) K₂Nb₄O₁₁—N.

FIG. 5. XPS spectra of the elements in K₂Nb₄O₁₁ (A) and K₂Nb₄O₁₁—N (B). 1, 2 and 3 refer to Nb, O and N, respectively.

FIG. 6. A) UV-vis diffuse reflectance spectra of K₂Nb₄O₁₁ and K₂Nb₄O₁₁—N; B) The curve deduced from A according to the equation (ahv)²=A(hv−E_(g)).

FIG. 7. Photoluminescence (Ph) emission spectra of (a) K₂Nb₄O₁₁ and (b) K₂Nb₄O₁₁—N.

FIG. 8. Plot of C/C_(o) (C is the concentration at time t, C_(o) is the initial concentration) versus time for the photo-degradation of OG using 330 nm cut off filter with a) K₂Nb₄O₁₁, b) K₂Nb₄O₁₁—N and c) TiO₂ P25.

FIG. 9. Plot of C/C_(o) (C is the concentration at time t, C_(o) is the initial concentration) versus time for photo-degradation of OG using 399 nm cut off filter with a) K₂Nb₄O₁₁, b) TiO₂ P25 and c) K₂Nb₄O₁₁—N.

FIG. 10. Spectral changes of OG during irradiation using 399 nm cutoff filter with K₂Nb₄O₁₁—N.

FIG. 11. Plot of (TOC)/(TOC)_(o) [(TOC) is the total organic carbon at time t, (TOC)_(o) is the initial total organic carbon] versus time for photo-degradation of OG using a 399 nm cut off filter with K₂Nb₄O₁₁—N.

FIG. 12. Plot of C/C_(o) (C is the concentration at time t, C_(o) is the initial concentration) versus time for photo-degradation of OG using a 399 nm cut off filter with a) Aged K₂Nb₄O₁₁—N; b) Fresh K₂Nb₄O₁₁—N.

FIG. 13. Plot of C/C_(o) (C is the concentration at time t, C_(o) is the initial concentration) versus time for photo-degradation of BPA using a 399 nm cutoff filter with a) no catalyst; b) Nb₂O₅; c) K₂Nb₄O₁₁; d) Degussa TiO₂ P25; e) K₂Nb₄O₁₁—N.

FIG. 14. Scheme of the band structure of K₂Nb₄O₁₁—N and visible photocatalytic processes.

FIG. 15. Plot of C/C_(o) (C is the concentration at time t, C_(o) is the initial concentration) versus time for photo-degradation of BPA by K₂Nb₄O₁₁—N at different pH; a) pH3; b) pH6; c) pH10.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides more effective photocatalysis with sunlight by nitrogen doped A₂Nb₄O₁₁. Specifically; the efficiency of K₂Nb₄O₁₁—N for the photodegradation of organic pollutants under visible light (>399 nm) irradiation has been investigated by using Orange C (OG) and bisphenol A (BPA) as substrates. Orange G (OG), a synthetic azo dye with formula C₁₆H₁₀N₂Na₂O₇S₂ (7-hydroxy-8-phenylyazo-1,3-naphthalenedisulfonic acid disodium salt), is an endocrine disruptor.¹⁹⁻²⁹ It is a common reagent in molecular biology and is used in histology as a staining agent. Bisphenol A is also a known endocrine disruptor which has been widely used for the production of polycarbonate (PC) and epoxy resins used in food containers.³⁰⁻³² Its concentration in wastewaters is increasing, which has become a worldwide pollution problem.³² The molecular structures and the UV-Vis absorption spectra of OG and BPA are shown in FIG. 1. OG absorbs strongly in the visible region but BPA absorbs only in the UV region. The results of the photodegradation experiments of the present invention show that the K₂Nb₄O₁₁—N photocatalyst has a much higher visible light activity than pure K₂Nb₄O₁₁ or Nb₂O₅, and it is also more active than Degussa P25 TiO₂. These results indicate that the photoactivity, of K₂Nb₄O₁₁ has been profoundly increased by nitrogen doping.

In order to prepare the nitrogen doped photocatalyst having the general formula A₂Nb₄O_(11-x)N_(x) to fulfill the object of the present invention, the process for the preparation thereof are exemplarily described with examples.

As the present invention may be embodied in several forms without departing from the spirit thereof, it should be understood that the embodiments of the present invention are not limited by any of the details of the description. Unless otherwise specified, it should be construed that all changes and modification of the embodiments of the present invention are within the scope as defined in the appended claims. Meanwhile, all the references cited in the present application are incorporated herein by reference in their entirety.

PREPARATION EXAMPLES Example 1

a) K₂Nb₄O₁₁ was prepared by heating a mixture of 0.2 g Nb₂O₅ and 0.8 g K₂CO₃ at 900° C. for 24 hours;

b) 1.0 g K₂Nb₄O₁₁ was immerged in 60 mL of 5 mol/L nitric acid solution for 48 hours, and then the product was filtered, washed with distilled water, and dried at 100° C. for 20 hours;

c) 10.0 g urea and 1.0 g K₂Nb₄O₁₁ were mixed and finely milled, and heated at 600° C. for 3 hours to provide a yellow product, which was washed with acetone to remove any residual alkaline species adsorbed on the surface of the product, and dried at 100° C. for 24 hours.

Example 2

a) K₂Nb₄O₁₁ was prepared by heating a mixture of 0.2 g K₂CO₃ and 0.8 g Nb₂O₅ at 900° C. for 24 hours;

b) 1.0 g K₂Nb₄O₁₁ was immerged in 60 mL of 5 mol/L nitric acid solution for 48 hours, and then the product was filtered, washed with distilled water, and dried at 100° C. for 20 hours;

c) 10.0 g K₂Nb₄O₁₁ and 2.0 g urea were finely milled, and heated at 400° C. for 4 hours. The resulted yellow product was washed with acetone and distilled water, and dried at 70° C. for 24 hours.

Example 3

a) K₂Nb₄O₁₁ was prepared by heating a mixture of 0.2 g K₂CO₃ and 0.8 g Nb₂O₅ at 1100° C. for 10 hours;

b) 1.0 g K₂Nb₄O₁₁ was immerged in 300 mL of 3 mol/L hydrochloric acid solution for 48 hours, and then the product was filtered, washed with distilled water, and dried at 100° C. for 20 hours;

c) 1.0 g K₂Nb₄O₁₁ and 10.0 g ammonium bicarbonate were finely milled, and heated at 400° C. for 4 hours. The resulted yellow product was washed with acetone and distilled water, and dried, at 70° C. for 24 hours.

Example 4

a) Na₂Nb₄O₁₁ was prepared by heating a mixture of 0.2 g Na₂CO₃ and 0.8 g Nb₂O₅ at 900° C. for 24 hours;

b) 1.0 g Na₂Nb₄O₁₁ was immerged in 3060 mL of 3 mol/L nitric acid solution for 96 hours, and then the product was filtered, washed with distilled water, and dried at 300° C., for 10 hours;

c) 1.0 g Na₂Nb₄O₁₁ and 0.5 g urea were finely milled, and heated at 400° C. for 24 hours. The resulted yellow product was washed with acetone, and dried at 100° C. for 24 hours.

Example 5

a) Na₂Nb₄O₁₁ was prepared by heating a mixture of 0.2 g Na₂CO₃ and 0.8 g Nb₂O₅ at 1100° C. for 24 hours;

b) 1.0 g Na₂Nb₄O₁₁ was immerged in 60 mL of 5 mol/L nitric acid solution for 48 hours, and then the product was filtered, washed with distilled water, and dried at 100° C. for 24 hours;

c) 1.0 g Na₂Nb₄O₁₁ and 10.0 g urea were finely milled, and heated at 400° C., for 6 hours. The resulted yellow product washed with acetone, and dried at 100° C. for 24 hours.

Example 6

a) Na₂Nb₄O₁₁ was prepared by heating a mixture of 0.2 g Nb₂O₅ and 0.8 g Na₂CO₃ at 900° C. for 24 hours;

b) 1.0 g Na₂Nb₄O₁₁ was immerged in 60 mL of 5 mol/L nitric acid solution for 48 hours, and then the product was filtered, washed with distilled water, and dried, at 100° C. for 20 hours;

c) 10.0 g urea and 1.0 g Na₂Nb₄O₁₁ were mixed and finely milled, and heated at 400° C. for 24 hours to provide a yellow product, which was washed with acetone to remove any residues adsorbed on the surface of the product, and dried at 100° C. for 24 hours.

Test Examples

The nitrogen doped. K₂Nb₄O₁₁ used in the test Examples is K₂Nb₄O₁₁—N prepared in Example 2.

1. Characterization of the Compound Having the General Formula (I)

The instruments for characterization include: powder X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), UV/Vis diffuse reflectance and photoluminescence spectroscopy (PL). The XRD analysis was performed on a Rigaku D-max X-ray diffractometer with Cu K_(α) irradiation (λ=1.5406 Å) at a scanning speed of 0.025°/sec over the scanning range of 20-70°. The morphologies were examined by a Philips XL30 environmental scanning electron microscope (ESEM) at an accelerating voltage of 10 kV. The surface analysis was done with a Leybold Heraeus-Shengyang SKL-12 electron spectrometer equipped with a VG CLAM 4 MCD electron energy analyzer, with Al—Kα as the excitation source. UV-Vis diffuse reflectance was performed on a Perkin Elmer Lambda 750 UV-Vis Spectrophotometer. Photoluminescence (PL) spectra were measured using a FluoroMax-3 spectrofluorimeter equipped with a pulsed xenon lamp as light source.

2. Photo-Catalytic Degradation Measurements

A 200 W xenon arc lamp (Newport, Model 71232) was used as the light source. OG or BPA aqueous solution (30 ml, 20 mg/L) and the photocatalyst (˜10 mg, nitrogen doped K₂Nb₄O₁₁ prepared in Example 2) were placed into a quartz tube reactor (12 mm in diameter and 200 mm in length) and the mixture was sonicated for 5 minutes to disperse the catalyst in the OG or BPA aqueous solution. The distance between the liquid surface and the light source was about 11 cm. Before the photoirradiation, the mixture was stirred in the dark for one hour so as to establish adsorption-desorption equilibrium on the surface of the catalyst for OG or BPA. The Infrared and UV light emitted from the Xe-lamp was filtered by a water jacket and a cutoff filter (Scott AG KV 399). Samples were collected at regular time intervals and centrifuged before Analysis. The concentrations of OG or BPA were measured with a Shimadzu UV-1700 UV-Vis spectro-photometer, wherein the OG or BPA concentration is proportional to its absorbance.

3. Results and Discussion 3.1 XRD

Powder X-ray diffraction (XRD) shows nearly identical patterns for K₂Nb₄O₁₁ and K₂Nb₄O₁₁—N prepared in Example 2. Typical XRD patterns of K₂Nb₄O₁₁ and K₂Nb₄O₁₁—N are shown in FIGS. 2A and 2B, respectively. For K₂Nb₄O₁₁ (FIG. 2A), all the diffraction peaks can be indexed as a tetragonal tungsten bronze structure (JCPDS 31-1059) with lattice constants of a=0.126 nm and c=0.398 nm. The XRD pattern of nitrogen doped K₂Nb₄O₁₁ nearly identical to that of undoped sample, as shown in FIG. 2B, indicating that there is no effect of nitrogen doping on the crystal structure of K₂Nb₄O₁₁, which suggests that (loping occurs only on the surface.

3.2 SEM

The SEM photographs of K₂Nb₄O₁₁ and K₂Nb₄O₁₁—N are shown in FIGS. 3A and 3B, respectively. FIG. 3A shows that the sizes and shapes of particles are inhomogeneous and the surface is clean. However, when K₂Nb₄O₁₁ was heated together with urea at 400° C., the surface of the sample became flock-like, but the sizes and shapes of the particles were not significantly changed. The SEM and XRD results together indicate that nitrogen doping does not affect the morphology and crystal structure of K₂Nb₄O₁₁, but affects the surface profile of the sample, as nitrogen doping occurs mainly on the surface of the sample,

3.3 XPS

The X-ray photoelectron spectroscopy (XPS) analysis is an important method to determine the composition and the chemical state of the elements. The XPS spectra of K₂Nb₄O₁₁ and K₂Nb₄O₁₁—N in wide energy range are shown in FIG. 4. No significant contamination, besides carbon, is found in the spectra. The binding energy was determined by reference to C 1s line at 284.8 eV. In the whole energy range spectrum shown in FIG. 4, the elements K, Nb and O can be observed in K₂Nb₄O₁₁ and K₂Nb₄O₁₁—N. However, N can only be seen in K₂Nb₄O₁₁—N, indicating successful doping of N onto the surface of K₂Nb₄O₁₁. The N concentration is calculated to be 3.9 atom % using the equation,

$C_{N} = \frac{\frac{I_{N}}{S_{N}}}{\sum\limits_{i}\frac{I_{i}}{S_{i}}}$

Where C_(N) is the nitrogen concentration, I_(N) and I_(i) are the peak intensities of nitrogen and other elements, respectively; S_(N) and S_(i) are the relative sensitivity factors of nitrogen and other elements, respectively.

To further determine the chemical states of the elements Nb, O and N, core level XPS spectra of K₂Nb₄O₁₁ and K₂Nb₄O₁₁—N are shown in FIG. 5. FIG. 5-A1 and B1 show that the binding energies of Nb 3d_(5/2) for K₂Nb₄O₁₁ and K₂Nb₄O₁₁—N are 206.8 and 206.9 eV, respectively, which are consistent with the reported values.³³ The chemical shifts of the binding energies of Nb 3d_(5/2) in these two materials are small. However, the full widths at half maximum (FWHM) of the Nb 3d_(5/2) peaks are different. The FWHM of Nb 3d_(5/2) for K₂Nb₄O₁₁ and K₂Nb₄O₁₁—N is 1.7 and 1.9 eV, respectively. The broadening of the Nb 3d_(5/2) peak indicates that the electron density on the Nb atoms in K₂Nb₄O₁₁—N is higher than that in K₂Nb₄O₁₁.³⁴ The main O is peak at 530.8 and 530.6 eV in FIGS. 5 A2 and B2 are assigned to lattice oxygen of K₂Nb₄O₁₁ and K₂Nb₄O₁₁—N, respectively.^(35,36) A higher binding energy shoulder is found for both samples at about 532.6 eV, this is assigned to a mixture of surface hydroxyl and carbonate groups.³⁶ Nitrogen is found only on K₂Nb₄O₁₁—N and the core-level N1s XPS is shown in FIG. 5-B3. The N1s spectrum is divided into two components with peak energies of 398.7 and 400.8 eV, respectively, which are assigned to be (N)_(i)/(NO)_(O) and (NO)_(i)/(NO₂)_(O), respectively.³⁷ (N)_(i) represents N in the interstitial space, (NO)_(O) denotes NO sitting at the site for the lattice O. Similarly, (NO)_(i) and (NO₂)_(O) designate the interstitial NO and substitutional NO₂ for the lattice O, respectively.

3.4 UV-Vis Diffuse Reflectance

The light absorption of the samples can be measured with UV/Vis diffuse reflectance spectroscopy.³⁵ FIG. 6 shows the UV/Vis diffuse reflectance spectra of K₃Nb₄O₁₁ and K₇Nb₄O₁₁—N. It is known that the optical absorption coefficient near the band edge follows the equation (ahv)²=A(hv−E_(g)), wherein a, h, v, E_(g) and A are the absorption coefficient, Planck constant, light frequency, band gap, and a constant, respectively.³⁸ From this equation, the band gaps can be calculated to be 3.27 eV and 3.12 eV for K₂Nb₄O₁₁ and K₂Nb₄O₁₁—N, respectively. The red-shift of the absorption wavelength of K₂Nb₄O₁₁—N compared with that of K₂Nb₄O₁₁, indicating that nitrogen-doping has a narrowing effect on the band gap of the material.³⁸

3.5 Photoluminescence (PL)

Photoluminescence emission spectra of semiconductors are related to the transport/relaxation behavior of the photo-induced electrons and holes, and thus can be used to determine band gaps, and to detect impurities and defects.³⁹ In order to study the effect of nitrogen doping on the band gap of K₂Nb₄O₁₁, PL spectra are shown in FIG. 7. There is a peak at about 370 nm for both K₂Nb₄O₁₁ and K₂Nb₄O₁₁—N, which is due to the band gap of K₂Nb₄O₁₁ crystals. On the other hand, K₂Nb₄O₁₁—N has an additional broad emission peak from 380 to 600 nm,⁴⁰⁻⁴² which confirms the effect of nitrogen doping narrowing the band gap of K₂Nb₄O₁₁—N.

3.6 Photocatalytic Degradation of Orange G by UV and Visible Light

The results of the photo-degradation of OG using K₂Nb₄O₁₁ and K₂Nb₄O₁₁—N as photocatalysts are shown in FIG. 8. The degradation of OG was negligible after 4 h when K₂Nb₄O₁₁ was used as the photocatalyst. On the other hand, when K₂Nb₄O₁₁—N was used, nearly 90% OG was degraded after 2 h of irradiation, indicating that nitrogen doping greatly enhances the photocatalytic activity of the K₂Nb₄O₁₁. Control experiments show that both light and the photocatalyst are required for the degradation of OG. The degradation of OG by K₂Nb₄O₁₁—N is only slightly less efficient than TiO₂ P25 when 330 nm cutoff filter is used. On the other hand, when 399 nm cutoff filter is used, the photocatalytic activity of K₂Nb₄O₁₁—N is much higher than that of TiO₂ P25. As shown in FIG. 9, nearly 90% of OG is degraded over the K₂Nb₄O₁₁—N after 12 h of photoirradiation when a 399 nm cutoff filter is used, while only 46% is degraded over TiO₂ P25.

FIG. 10 shows the spectral changes of OG during irradiation using 399 am cutoff filter with K₂Nb₄O₁₁—N. The main absorption band of OG is at around 478 nm, which decreases with time upon irradiation, but the λ_(max) does not change, indicating that the photodegradation does not occur by a dye self-photosensitized oxidative mechanism.⁴³ Apart from the peak at 478 nm, the photodegradation of OG by K₂Nb₄O₁₁—N also results in the disappearance of the peak at 330 nm, indicating that both the OG chromophores and the aromatic rings have been destroyed.¹³ Also the total organic carbon (TOC) value of the solution decreases by approximately 25% at 90% OG conversion after 12 h of irradiation (see FIG. 11), indicating that OG is mainly degraded to aliphatic organic compounds and is only partially mineralized to CO₂ and/or CO.

To assess the stability of the photocatalyst, a sample of K₂Nb₄O₁₁—N was aged under ambient conditions for six months and its photocatalytic activity was then tested. As shown in FIG. 12, the photocatalytic activity of the aged K₂Nb₄O₁₁—N sample decreases by only about 6% compared with the freshly prepared sample, indicating that K₂Nb₄O₁₁—N photocatalyst is reasonably stable when stored under ambient conditions.

3.7 Photocatalytic Degradation of BPA by Visible Light

It has been suggested by several authors that the photocatalytic degradation of dyes under visible light may be induced by self-photosensitization of the dye rather than by the catalyst.^(44,45) In order to understand the photoactivity of K₂Nb₄O₁₁—N under visible light, Bisphenol A (BPA), which is a colorless pollutant, was selected as another probe substrate. For comparison, Nb₂O₅, pure K₂Nb₄O₁₁ and Degussa TiO₂ P25 were also used as photocatalysts and the results are shown in FIG. 13.

In the absence of a photocatalyst, the concentration of BPA remained virtually unchanged even after 20 h of visible light irradiation (399 nm cutoff). Also, BPA was not degraded by the photocatalysts in the dark. However, upon visible light irradiation in the presence of K₂Nb₄O₁₁—N, 90% of BPA was degraded after 6 h. This photoactivity is higher than that of Degussa TiO₂ P25, and is much higher than that of pure K₂Nb₄O₁₁ and Nb₂O₅. These results confirm that nitrogen doping greatly enhances the photoactivity of K₂Nb₄O₁₁.

3.8 Mechanism for the Photocatalytic Activity of K₂Nb₄O₁₁—N

Taking K₂Nb₄O₁₁—N as an example, the band structure for the K₂Nb₄O₁₁—N is proposed, as schematically shown in FIG. 14. In the K₂Nb₄O₁₁—N photocatalyst, there exist isolated N 2p states above the valence-band maximum of K₂Nb₄O₁₁, which give rise to the strong absorption enhancement in the visible region. Under visible light irradiation, electron and hole pairs would be generated between impurity N 2p states and the conduction band of Nb 4d (equation 1).

K₂Nb₄O₁₁—N+visible light

h ⁺ +e ⁻ _(CB)  (1)

The excited electrons e⁻ _(CB) in the conduction band would move to the surface and combine with surface-adsorbed oxygen to produce O₂ ^(.−) superoxide anion radicals. The O₂ ^(.−) could then react with H₂O to produce .OH radicals (equation 2),⁵²′⁵³ which are known to be one of the most oxidizing species. On the other hand, the reactive holes h⁺ would react with adsorbed OH⁻ on the catalyst surface to also form .OH radicals (equations 3-4).^(52,53)

O_(2ads) ^(.−)+2H₂O→.OH⁻+H₂O₂  (2)

H₂O

OH⁻ _(ads)+H⁺  (3)

OH_(ads) ⁻ +h ⁺→.OH  (4)

The .OH radicals would react with OG and BPA to produce H₂O and CO₂ via various intermediates.

In order to provide more evidence to support the proposed mechanism, the effects of pH on the photocatalytic degradation of BPA by K₂Nb₄O₁₁—N were also studied (see FIG. 15). It was found that photocatalytic activity of K₂Nb₄O₁₁—N increases when the solution pH decreases. This may be explained by the processes shown in equations 5-7, which occur in the presence of H⁺.

O_(2ads) ^(.−)+H⁺→HO_(2ads) ^(.)  (5)

HO_(2ads) ^(.)+H₂O→.OH_(ads)+H₂O_(2ads)  (6)

H₂O_(2ads) +e _(CB) ⁻→.OH_(ads)+OH_(ads) ⁻  (7)

These processes facilitate trapping of the electrons in the conduction band of K₂Nb₄O₁₁—N which produces .OH_(ads). This trapping mechanism retards the recombination of electron-hole pairs and allows a more efficient charge separation. Hence, the transfer of trapped electrons to dissolved oxygen in the solution would be enhanced and more holes and hydroxyl radicals would be available for the oxidation of BPA on the catalyst surface as well as in the solution phase. This pH effect supports our proposed mechanism for the photocatalytic activity of K₂Nb₄O₁₁—N under visible light.

4. Conclusions

In the present invention, A₂Nb₄O₁₁—N has been prepared, fully characterized and used for the photodegradation of OG and BPA. XRD and SEM show that the crystal structures of K₂Nb₄O₁₁—N and K₂Nb₄O₁₁ are nearly identical, but the surface profile has been changed significantly due to the nitrogen doping. XPS and PL indicate that the nitrogen doping primarily occurs at the surface of K₂Nb₄O₁₁, while UV/Vis diffuse reflectance data further reveal that nitrogen doping narrows the band gap of K₂Nb₄O₁₁. The photocatalytic activity of the K₂Nb₄O₁₁—N has been evaluated by photodegradation of OG and BPA under visible light irradiation. The results show that the photocatalytic activity of K₂Nb₄O₁₁—N is significantly higher than that of pure K₂Nb₄O₁₁ and Degussa TiO₂ P25 under visible light irradiation, highlighting the importance of nitrogen doping of K₂Nb₄O₁₁. Overall, we have for the first time prepared and characterized A₂Nb₄O₁₁—N with high photocatalytic activity even with visible light illumination. Moreover, this photocatalyst is very stable (at least six months under ambient conditions), its preparation is simple and highly reproducible, and it is easy to separate from the solution by simple centrifugation.

REFERENCES

-   1. M. A. Behnajady, N. Modirshahla, R. Hamzavi, J. Hazard. Mater., B     2006, 133 226-232, -   2, A. Akyol, H. C. Yatmaz, M. Bayramoglu, Appl. Catal. B, 2004, 54,     19-24. -   3. R. Kavitha, S. Meghani, V. Jayaram, Mater. Sci. Eng. B, 2007,     139, 134-140. -   4. R. Y. Hong, J. H. Li, L. L. Chen, D. Q. Liu, H. Z. Li, Y.     Zheng. J. Ding, Powder Technol., 2009, 189, 426-432, -   5. P. Pawinrat, O. Mekasuwandumrong, J. Panpranot, Catal. Commu.,     2009, 10, 1380-1385. -   6. X. Zhou, Y. Z. Li, T. Peng, W. Xie, X. J. Zhao, Mater. Lett.,     2009, 63, 1747-1749. -   7. R. A. Damodar, S. J. You, H. H. Chou, J. Hazard. Mater., 2009,     172, 1321-1328. -   8. Z. B. Wu, F. Dong, Y. Liu, H. Q. Wang, Catal. Commun., 2009, 11,     82-86. -   9. A. Vijayabalan, K. Selvam, R. Velmurugan, M. Swaminathan, J.     Hazard. Mater., 2009, 172, 914-921. -   10. L. W. Zhang, Y. J. Wang, H. Y. Cheng, W. Q. Yao, Y. F. Zhu, Adv.     Mater., 2009, 21, 1286+. -   11. H. Y. Zhu, R. Jiang, L. Xiao, Y. H. Chang, Y. J. Guan X. D.     Li., G. M. Zeng, J. Hazard. Mater., 2009, 169, 933-940. -   12. E. Rodriguez, G. Fernandez, B. Ledesma, P. Alvarez, F. J.     Beltran, Appl. Catal. B Envir., 2009, 92, 240-249. -   13. X. Li, N. Kikugawa, J. Ye, Chem. Eur. J., 2009, 15, 3538-3545. -   14. M. Dion, M. Ganne, M. Tournoux, Mat. Res. Bull, 1981, 16,     1429-1435. -   15. J. Yoshimura, Y. Ebina, J. Kondo, K. Domen, A. Tanaka, J. Phys.     Chem., 1993, 97, 1970-1973. -   16. J. H. Wu, Y. H. Cheng, J. M. Lin, Y. F. Huang, M. L.     Huang, S. C. Hao, J. Phys. Chem. C, 2007, 111, 3624-3628. -   17. M. Lundberg, M. Sundberg, J. Solid State Chem., 1986, 63,     216-230. -   18. G. K. Zhang, X. Zou, J. Gong, F. He, H. Zhang, S. Ouyang, H.     Liu, J. Molec. Catal. A: Chem., 2006, 255, 109-116. -   19. B. Muktha, G. Madras, T. N. G. Row, U. Scherf, S. Patil,     Conjugated polymers for photocatalysis, J. Phys. Chem., B, 2007,     111, 7994-7998. -   20. P. Mahata, G. Madras, S. Natarajan, Catal. Lett., 2007, 115,     27-32. -   21. P. Mahata, G. Madras, S. Natarajan, J. Phys. Chem. B, 2006, 110,     13759-13768. -   22. S. Mahapatra, G. Madras, T. N. Guru Row, J. Phys. Chem., C.     2007, 111, 6505-6511. -   23. M. Sokmen, A. Ozkan, J. Photochem. Photobiol. A-Chem., 2002,     147, 77-81. -   24. C. Guillard, H. Lachheb, A. Houas, M. Ksibi, E. Elaloui, J.-M.     Herrmann, J. Photochem. Photobiol. A-Chem., 2003, 158, 27-36. -   25. J. Sun, X. Wang, J. Sun, R. Sun, S. Sun, L. Qiao, J. Mol. Catal.     A-Chem., 2006, 260, 241-246. -   26. J. M. Kwon, Y. H. Kim, B. K. Song, S. H. Yeom, B. S. Kim, J. B.     Im, J. Hazard. Mater., 2006, 134, 230-236. -   27. G. Sivalingam, K. Nagaveni, M. S. Hegde, G. Madras, Appl. Catal.     B-Environ., 2003, 45, 23-38. -   28. C. Hachem, F. Bocquillon, O. Zahraa, M. Bouchy, Dyes Pigment.,     2001, 49, 117-125; S. Yang, L. Lou, K. Wang, Y. Chen, Appl. Catal.     A-Gen., 2006, 301, 152-157. -   29. K. Nagaveni, G. Sivalingam, M. S. Hegde, G. Madras, Appl. Catal.     B-Environ., 2004, 48, 83-93; J. H. Sun, L. P. Qiao, S. P. Sun, G. L.     Wang, Journal of Hazard. Mater., 2008, 155, 312-319. -   30. R. Tsekov, E. Evstatieva, K. W. Stockelhuber, P. G. Smirniotis,     Progr Colloid Polym Sci., 2004, 126, 117-120; D. Beydoun, R.     Amal, G. K.-C. Low, S. McEvoy, J. Phys. Chem. B, 2000, 104,     4387-4396. -   31. G. K. Zhang, X. Zou, J. Gong, F. He, H. Zhang, S. Ouyang, H.     Liu, J. Molec. Catal. A: Chem., 2006, 255, 109-116; B. Muktha, G.     Madras, T.N.G. Row, U. Scherf, S. Patil, Conjugated polymers for     photocatalysis, J. Phys. Chem. B. 2007, 111, 7994-7998. -   32. P. Mahata, G. Madras, S. Natarajan, Catal. Lett., 2007, 115,     27-32. -   33. G. K. Zhang, Y. J. Hu, X. M. Ding, J. Zhou, J. W. Xie, J. Solid     Sate Chem., 2008, 181, 2133-2138. -   34. T. Shishido, M. Oku, S. Okada, K. Kudou, J. Ye, T. Sasaki, Y.     Watanabe, N. Toyota, H. Horiuchi, T. Fukuda, J. Alloy. Comp., 1998,     281, 196-201. -   35. A. Molak, E. Tank, M. Kruczek, M. Paluch, A. Ratuszna, Z. Ujma,     Mater Sci. and Engl. B, 2006, 128, 16-24. -   36. S.-Y. Lai, Y. Qiu, S. Wang, J. Catal., 2006, 237, 303-313. -   37, R. Asahi, T. Morikawa, Chem. Phys., 2007, 339, 57-63. -   38. M. A. Butler, J. Appl. Phys., 1997, 48, 1914-1920. -   39. Y. C. Zhu, C. X. Ding, J. Solid State Chem., 1999, 145, 711-715. -   40. C. Yu, J. C. Yu, Catal. Lett., 2009, 129, 462-470. -   41. Y. Qiu, S. Yang, Advanced Functional Materials, 2007, 17,     1345-1352. -   42, J. C. Yu, J. G. Yu, W. K. Ho, Z. T. Jiang, L. Z. Zhang, Chem.     Mater., 2002, 14, 3808-3816. -   43, T. Wu, G. Liu, J. Zhao, H. Hidaka, N. Serpone, J. Phys. Chem.,     B, 1998, 102, 5845-5851, -   44. M. R. Hoffmann, S. T. Martin, W. Y. Choi., D. W. Bahnemann,     Chem. Rev., 1995, 95, 69-96; A. Mills, J. S. Wang, J. Photochem.     Photobiol. A., 1999, 127, 123-134; M. Mrowetz, W. Baleerski, A. J.     Colussi, M. R. Hoffmann, J. Phys. Chem. B., 2004, 108, 17269-17273. -   45, X, L. Yan, T. Ohno, K. Nishijima, R. Abe, B. Ohtani, Chem. Phys.     Lett., 2006, 429, 606-610; B. Ohtani, Chem. Lett., 2008, 37,     217-229; G. S. Wu, T. Nishikawa, B. Ohtani, A. C. Chen, Chem.     Mater., 2007, 19, 4530-4537; R. Abe, H. Takami, N. Murakami, B.     Ohtani, J. Am. Chem. Soc., 2008, 130, 7780-7781; F. Amano, O.-O.     Prieto-Mahaney, Y. Terada, T. Yasumoto, T. Shihayama, B. Ohtani,     Chem. Mater., 2009, 21, 2601-2603; F. Amano, A. Yamakata, K.     Nogami, M. Osawa, B. Ohtani, J. Am. Chem. Soc., 2008, 130,     17650-17651. -   46. K. Nagaveni, M. S. Hegde, N. Ravishankar, G. N. Subbanna, G.     Madras, Langmuir, 2004, 20, 2900-2907. -   47. F. Dong, W. R. Zhao, Z. B. Wu, S. Guo, J. Hazar: Mater., 2009,     162, 763-770. 

1. A compound, which is a nitrogen doped A₂Nb₄O₁₁ represented by the following general formula (I) A₂Nb₄O_(11-x)N_(x)  (I) wherein A is selected from the elements of IA group of the periodic table; and 0<x<1.
 2. The compound of claim 1, wherein A is Li, Na, K, Rb or Cs.
 3. The compound of claim 1, wherein the compound has a tetragonal tungsten bronze crystal structure.
 4. The compound of claim 1, wherein the compound is a photocatalyst.
 5. The compound of claim 4, wherein the photocatalyst is activated under visible lights.
 6. A process for the preparation of the compound of claim 1, comprising the steps of: 1) surface acidification of A₂Nb₄O₁₁, wherein A₂Nb₄O₁₁ is immerged in an acidic solution, filtered, washed and dried; and 2) nitrogen doping of A₂Nb₄O₁₁ to obtain A₂Nb₄O_(11-x)N_(x), wherein A₂Nb₄O₁₁ obtained in step 1) is mixed with a nitrogen source and heated, the product is washed to remove residue nitrogen source adsorbed on the surface of the product and dried.
 7. The process of claim 6, wherein the acidic solution used in step 1) is selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, or phosphoric acid.
 8. The process of claim 7, wherein the acidic solution has a concentration of 1-10 mol/L.
 9. The process of claim 8, wherein, in step 1), the ratio of the weight of A₂Nb₄O₁₁ to the volume of the acidic solution is from 1 g:10 ml to 1 g:600 ml, and the duration of the immerging is 10-96 h.
 10. The process of claim 6, wherein the nitrogen source is an ammonium salt or a nitrogen-containing organic compound.
 11. The process of claim 10, wherein the nitrogen source is urea or ammonium carbonate.
 12. The process of claim 6, wherein, in step 2), the weight ratio of A₂Nb₄O₁₁ and the nitrogen source is from 1:0.5 to 1:10.
 13. The process of claim 6, wherein, in step 2), the heating is performed under a temperature of 300-600° C., and the duration of the heating is 1-10 h.
 14. The process of claim 6, wherein, in step 2), the product is washed with acetone and/or distilled water, and dried under a temperature of 20-300° C. for 10-96 h.
 15. The process of claim 14, wherein the product is washed with distilled water, and dried under a temperature of 20-300° C. for above 10 h.
 16. A method for degradation of organic pollutants, comprising contacting the organic pollutants with the compound of claim
 1. 17. The method of claim 16, wherein the organic pollutants are those difficult to decompose in waste water. 